This invention relates to processes for preparing poly(oxyalkylene) polymers and to methods for preparing same.
Polyethers made from alkylene oxides are well known and useful in a number of applications such as detergent and cleaner compositions, oil well drilling fluids, inks, metal working fluids, lubricants in paper coating compositions, ceramics manufacturing, chemical intermediates for nonionic surfactants which in turn are used in cosmetics, textiles and chemical processing, polyurethanes which are used as flexible foams and elastomers, chemical intermediates for esters which are used in textile spin finishes, cosmetic agents, and as foam control agents for a wide variety of processes. These polymers may have no more than one oxyalkylene group in succession, or be a higher molecular weight polymer containing one or more long chains of consecutive oxyalkylene groups.
Polyethers of this type are commonly made through an anionic polymerization process, whereby the alkylene oxide is combined with an initiator compound and a strongly basic catalyst such as potassium hydroxide or certain organic amines. The initiator compound contains one or more oxyalkylatable groups such as hydroxyl, thiol, carboxylic acid and the like. The initiator compound determines the functionality (i.e., number of hydroxyl groups/molecule of product) and in some cases may introduce some desired functional group into the product.
There are some disadvantages of polymerizing alkylene oxides using these strongly basic catalysts. One problem is that the strongly basic catalysts do not produce a low polydispersity product when a tertiary alcohol initiator compound is used. In addition, the basic catalyst usually must be removed from the product before it is used, which increases manufacturing costs.
In addition, some kinds of initiator compounds cannot be alkoxylated using strongly basic catalysts, because they contain base-sensitive functional groups. For example, initiators containing certain types of alkenyl or alkynyl groups undergo a side reaction in which the alkenyl or alkynyl group will xe2x80x9cmigratexe2x80x9d along the molecular chain, so that the unsaturation in the polyether is at a different place than it was on the initiator. This is of particular concern when terminal unsaturation is desired. Often, unsaturation that is in a terminal position on the initiator migrates to a non-terminal position during the alkoxylation reaction.
Unsaturated compounds in which a triple bond is adjacent to a hydroxyl-substituted carbon atom are prone to decomposing during the alkoxylation reaction. Many compounds of this type are reaction products of acetylene with a ketone such as acetone or an aldehyde such as acetaldehyde. Alkali metal or alkaline earth bases can cause these initiators to decompose to regenerate acetylene. Acetylene is an explosion hazard.
In order to try to avoid these problems, Lewis acids such as boron trifluoride-diethyl etherate and organic amines such as triethylamine have been tried. However, some of these catalysts tend to promote the formation of large amounts of by-products, especially when it is attempted to add three or more moles of alkylene oxide per equivalent of initiator compound. The Lewis acid catalysts tend to catalyze xe2x80x9cback-bitingxe2x80x9d reactions where the growing polymer chain reacts with itself. The reactions form cyclic ethers such as dioxane, dimethyldioxane and various crown ethers. These cannot be removed easily from the desired product, and so the product cannot be used in many applications.
Thus, it would be desirable to provide a method whereby polyethers made using certain unsaturated initiator compounds could be produced in good yield with low levels of by-products.
In one aspect, this invention is a process for preparing a polyether, comprising forming a mixture of an initiator compound having one or more oxyalkylatable groups, at least one alkylene oxide and a metal cyanide catalyst complex, and subjecting the mixture to conditions sufficient to activate the catalyst complex and to alkoxylate the oxyalkylatable groups of the initiator, wherein the initiator compound contains nonconjugated carbon-carbon unsaturation that is (a) migratable, as defined below, (b) adjacent to a hydroxyl-substituted tertiary carbon atom, or both (a) and (b).
In a second aspect, this invention is a poly(alkylene oxide) polymer containing the residue of an initiator compound having nonconjugated carbon-carbon unsaturation that is (a) migratable, as defined below, (b) adjacent to a hydroxyl-substituted tertiary carbon atom, or both (a) and (b), the polymer having an average alkoxy degree of polymerization of at least three moles of alkylene oxide per equivalent of initiator compound.
This invention permits the ready formation of polymers of unsaturated initiators containing certain types of carbon-carbon unsaturation that tend to engage in side-reactions during previous alkoxylation processes. The product polymers contain desired, predetermined types of carbon-carbon unsaturation that are predictable from the selection of the initiator compound.
In this invention, certain initiator compounds are alkoxylated by reaction with one or more alkylene oxides in the presence of a catalytically effective amount of a metal cyanide catalyst. The alkoxylation is conducted by combining the initiator, metal cyanide catalyst and alkylene oxide. The catalyst is then allowed to become activated in the presence of the alkylene oxide. Once the catalyst has become activated, the mixture is subjected to conditions sufficient to polymerize the alkylene oxide. In this manner, the initiator compound becomes alkoxylated until poly(oxyalkylene) chains of a desired length are introduced. As discussed below, once polymerization has begun, other types of monomers that are copolymerizable with alkylene oxides can be polymerized as well.
The initiator compound used in the process contains carbon-carbon unsaturation, i.e., a carbon-carbon double bond (i.e., an alkenyl group) and/or a carbon-carbon triple bond (i.e., an alkynyl group). The carbon-carbon unsaturation is not conjugated, i.e., is not part of a sequence of two or more double or triple bonds that alternate with single bonds. Thus, the carbon-carbon unsaturation is not part of an aliphatic hydrocarbyl conjugated structure (such as xe2x80x94CHxe2x95x90CHxe2x80x94(CHxe2x95x90CHxe2x80x94)x), part of an aromatic group, nor part of a conjugated structure including carbonyl groups (such as a xe2x80x94CRxe2x95x90CRxe2x80x94C(O)xe2x80x94 grouping, as is present, for example, in acrylic or methacrylic compounds, maleic acid, fumaric acid, and the like). In the forgoing structure, each R independently represents hydrogen or an unsubstituted or inertly substituted group hydrocarbon that is attached to the indicated carbon atom through a carbon-carbon single bond. By xe2x80x9cinertly substitutedxe2x80x9d, it is meant a group that does not react under the conditions of the alkoxylation process of the invention.
In addition, the carbon-carbon unsaturation is either migratable, adjacent to a hydroxyl-substituted tertiary carbon atom, an alkyne which is base sensitive or any combination of the above. In the case of a carbon-carbon double bond, xe2x80x9cmigratablexe2x80x9d means that the unsaturation is adjacent to a xe2x80x94CHR6xe2x80x94 group that is not substituted with any heteroatom, where R6 is hydrogen or an unsubstituted or inertly substituted alkyl group. Thus, a migratable alkenyl group would have the structure xe2x80x94CRxe2x95x90CRxe2x80x94CHR6xe2x80x94R1OH, where R is as defined above and R1 is an unsubstituted or inertly substituted alkylene group. A migratable alkynyl group is adjacent to a methylene group and would have the structure xe2x80x94Cxe2x89xa1Cxe2x80x94CH2xe2x80x94R1OH, where R1 is as defined above. Unsaturation of this type can xe2x80x9cmigratexe2x80x9d to the adjacent xe2x80x94CHR6xe2x80x94 or xe2x80x94CH2xe2x80x94 group under basic conditions. Thus, for example, the migratable alkenyl group shown above can isomerize to form a xe2x80x94CHRxe2x80x94CRxe2x95x90CR6xe2x80x94R1OH group under basic conditions. In the same way, the migratable alkynyl group shown above can isomerize to form a xe2x80x94CH2xe2x80x94Cxe2x89xa1Cxe2x80x94R1OH group. Among the initiators of this type, those in which the carbon-carbon unsaturation occupies a terminal position (i.e. those of the general structure H2Cxe2x95x90Cxe2x80x94CHR6xe2x80x94R1xe2x80x94OH or H2Cxe2x89xa1Cxe2x80x94CH2xe2x80x94R1xe2x80x94OH are of particular interest. Among the initiators of this type are 3-butyn-1-ol, 3-butene-1-ol, cyclohex-2-ene-1-ol and the like. Carbon-carbon unsaturation adjacent to a hydroxyl-substituted tertiary carbon atom can be represented by the structures 
where R is as defined above. These compounds are of particular interest because they form products having broad polydispersities under standard alkoxylation conditions with alkali or alkaline earth catalysis. Furthermore, alkyne unsaturation adjacent to a hydroxyl-substituted or alkoxy substituted carbon atom tends to decompose under basic conditions forming acetylene in some cases and creating an explosion hazard. Among the initiators of this type are 2-methyl-3-butyn-2-ol, 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3-butyn-2-ol, propargyl alcohol, 2-methyl-3-butyn-2-ol and the like, as well as other alkynyl tertiary alcohols that are formed in the reaction of acetylene and a ketone such as acetone in various proportions, and ethoxylated derivatives thereof.
The alkoxylation is performed by first mixing the initiator, catalyst and an alkylene oxide and allowing the mixture to sit for a period of time at room or an elevated temperature. When these materials are mixed, a so-called induction period occurs, during which the oxyalkylene reaction occurs very slowly. The induction period may range from a few minutes to several hours, depending on the particular catalyst that is used and the temperature. During this induction period, the catalyst becomes activated, and rapid polymerization of the alkylene oxide then commences.
The starting mixture of catalyst, initiator compound and alkylene oxide is conveniently made by combining the catalyst and initiator compound in a pressure reactor (or by forming the catalyst in the initiator), and then pressurizing the reactor with an initial quantity of alkylene oxide. The induction period follows, as indicated by a nearly constant or slowly decreasing pressure in the reactor. The onset of rapid polymerization that follows the induction period is evidenced by a drop in pressure as the alkylene oxide is consumed.
The starting mixture of catalyst, initiator compound and alkylene oxide may be brought to any convenient temperature, such as from about 20xc2x0 C., preferably from about 50xc2x0 C., more preferably from about 70xc2x0 C., even more preferably from about 80xc2x0 C. to about 150xc2x0 C., most preferably to about 100xc2x0 C. These temperatures are also suitable for conducting the polymerization once the catalyst is activated.
Depending on the desired degree of alkoxylation, all the necessary alkylene oxide may be added to the reactor at the outset. It is usually preferred to add more alkylene oxide to the reactor once the catalyst has become activated, especially when making higher molecular weight polyethers. A convenient way of adding the alkylene oxide is to pressurize the reactor with alkylene oxide and allow alkylene oxide to feed to the reactor on demand, maintaining a more or less constant pressure inside the reactor. Alternatively, any additional alkylene oxide may be fed in one or more discrete increments.
The total amount of alkylene oxide that is fed will depend on the desired equivalent weight of the product. As few as one mole of alkylene oxide per equivalent of initiator compound can be added. This invention is particularly suited for polymerizing at least about 3 moles of alkylene oxide per equivalent of initiator compound. Sufficient alkylene oxide can be added to make any desirable molecular weight polyether, such as one having a weight average molecular weight of 200,000 daltons or more. However, in most cases the intended end-use of the product will dictate its molecular or equivalent weight. Thus, for example, for making polyols for polyurethane applications, polyether equivalent weights of from about 75-500 are of particular interest for rigid polyurethane foams, equivalent weights of from about 300-1300 are of particular interest for making molded foams and high resiliency slabstock foams, and equivalent weights of from about 800-3000 are of particular interest for making conventional slabstock foam and reaction injection molded elastomers. For surfactant applications, molecular weights of from about 350 to about 6000 are of particular interest. In most applications, it is desirable that the product be a liquid. Poly(oxyethylene) homopolymers tend to form solids when their weight average molecular weights exceed about 700 daltons. Thus, when a poly(ethylene oxide) homopolymer is made in accordance with the invention, preferred molecular weights are about 1000 or below. All weights reported above are number average molecular weights.
Similarly, the selection of alkylene oxide will depend to a large extent on the intended end-use of the product. Among the alkylene oxides that can be polymerized with the catalyst complex of the invention are ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, and mixtures thereof. Mixtures of these can be used, and two or more of them can be polymerized sequentially to make block copolymers. For polyurethanes applications, preferred alkylene oxides are propylene oxide alone, mixtures of at least 50 weight % propylene oxide and up to about 50 weight % ethylene oxide (to form a random copolymer), and propylene oxide followed by ethylene oxide, so as to form terminal poly(oxyethylene) chains constituting up to about 30% of the total weight of the product. For other applications, ethylene oxide alone, 1,2-butylene oxide, ethylene oxide/1,2-butylene oxide mixtures, ethylene oxide followed by propylene oxide or butylene oxide, butylene oxide followed by ethylene and/or propylene oxide, propylene oxide alone, mixtures of propylene oxide and ethylene and/or butylene oxide, and propylene oxide followed by ethylene and/or butylene oxide are preferred alkylene oxides.
In addition, monomers that will copolymerize with the alkylene oxide in the presence of the catalyst complex can be used to prepare modified polyether polyols, after the catalyst has become activated. Such comonomers include oxetanes as described in U.S. Pat. Nos. 3,278,457 and 3,404,109 and anhydrides as described in U.S. Pat. Nos. 5,145,883 and 3,538,043, which yield polyethers and polyester or polyetherester polyols, respectively. Lactones as described in U.S. Pat. No. 5,525,702 and carbon dioxide are examples of other suitable monomers that can be polymerized with the catalyst of the invention.
The polymerization reaction may be performed continuously or batchwise. In such continuous processes, the activated initiator/catalyst mixture is continuously fed into a continuous reactor such as a continuously stirred tank reactor (CSTR) or a tubular reactor. A feed of alkylene oxide is introduced into the reactor and the product continuously removed.
An advantage of this invention is that no polymerization inhibitors are needed in order to prevent vinyl polymerization of the initiator compound. Similarly, there is no need to employ low alkoxylation temperatures in order to prevent vinyl polymerization.
The concentration of the catalyst is selected to polymerize the alkylene oxide at a desired rate or within a desired period of time. Generally, a suitable amount of catalyst is from about 5 to about 10,000 parts by weight metal cyanide catalyst complex per million parts of the product. For determining the amount of catalyst complex to use, the weight of the product is generally considered to equal the combined weight of alkylene oxide and initiator, plus any comonomers that may be used. More preferred catalyst complex levels are from about 10, especially from about 25, to about 5000, more preferably about 3000 ppm, on the same basis.
The metal cyanide catalyst can be represented by the general formula:
Mb[M1(CN)r(X)t]c[M2(X)6]dxc2x7zLxc2x7nM3xAy,
wherein M is a metal ion that forms an insoluble precipitate with the M1(CN)r(X)t group and which has at least one water soluble salt;
M1 and M2 are transition metal ions that may be the same or different;
each X independently represents a group other than cyanide that coordinates with an M1 or M2 ion;
L represents an organic complexing agent;
M3xAy represents a water-soluble salt of metal ion M3 and anion A, wherein M3 is the same as or different than M;
b and c are positive numbers that, together with d, reflect an electrostatically neutral complex;
d is zero or a positive number;
x and y are numbers that reflect an electrostatically neutral salt;
r is from 4 to 6; t is from 0 to 2;
z is zero or a positive number and n is a positive number indicating the relative quantities of the complexing agent and MxAy, respectively. z and n may be fractions.
The X groups in any M2(X)6 do not have to be all the same. The molar ratio of c:d is advantageously from about 100:0 to about 20:80, more preferably from about 100:0 to about 50:50, and even more preferably from about 100:0 to about 80:20.
Similarly, the catalyst may contain two or more types of M1(CN)r(X)t groups and two or more types of M2(X)6 groups.
M and M3 are preferably metal ions selected from the group consisting of Zn+2, Fe+2, Co+2, Ni+2, Mo+4, Mo+6, Al+3, V+4, V+5, Sr+2, W+4, W+6, Mn+2, Sn+2, Sn+4, Pb+2, Cu+2, La+3 and Cr+3. M and M3 are more preferably Zn+2, Fe+2, Co+2, Ni+2, La+3 and Cr+3. M is most preferably Zn+2.
Suitable anions A include halides such as chloride and bromide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, and a C1-4 carboxylate. Chloride ion is especially preferred.
M1 and M2 are preferably Fe+3, Fe+2, Co+3, Co+2, Cr+2, Cr+3, Mn30 2, Mn+3, Ir+3, Ni+2, Rh+3, Ru+2, V+4 and V+5. Among the foregoing, those in the plus-three oxidation state are more preferred. Co+3 and Fe+3 are even more preferred and Co+3 is most preferred.
Preferred groups X include anions such as halide (especially chloride), hydroxide, sulfate, C1-4 carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C1-4 carboxylate and nitrite (NO2xe2x80x94), and uncharged species such as CO, H2O and NO. Particularly preferred groups X are NO, NO2xe2x80x94 and CO.
The catalyst is usually complexed with an organic complexing agent. A great number of complexing agents are potentially useful, although catalyst activity may vary according to the selection of a particular complexing agent. Examples of such complexing agents include alcohols, aldehydes, ketones, ethers, amides, nitriles, sulfides, and the like.
Suitable alcohols include monoalcohols and polyalcohols. Suitable monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, octanol, octadecanol, 3-butyn-1-ol, 3-butene-1-ol, propargyl alcohol, 2-methyl-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-butene-2-ol, 3-butyn-1-ol, 3-butene-1-ol, 1-t-butoxy-2-propanol and the like. Suitable monoalcohols also include halogenated alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1,3-dichloro-2-propanol, 1-chloro-2-methyl-2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols, and other inertly substituted alcohols.
Suitable polyalcohols include ethylene glycol, propylene glycol, glycerine, 1,1,1-trimethylol propane, 1,1,1-trimethylol ethane, 1,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, sucrose, sorbitol, alkyl glucosides such as methyl glucoside and ethyl glucoside, and the like. Low molecular weight polyether polyols, particular those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful complexing agents.
Suitable aldehydes include formaldehyde, acetaldehyde, butyraldehyde, valeric aldehyde, glyoxal, benzaldehyde, toluic aldehyde and the like. Suitable ketones include acetone, methyl ethyl ketone, 3-pentanone, 2-hexanone and the like.
Suitable ethers include cyclic ethers such as dioxane, trioxymethylene and paraformaldehyde as well as acyclic ethers such as diethyl ether, 1-ethoxy pentane, bis(betachloro ethyl) ether, methyl propyl ether, diethoxy methane, dialkyl ethers of alkylene or polyalkylene glycols (such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and octaethylene glycol dimethyl ether), and the like.
Amides such as formamide, acetamide, propionamide, butyramide and valeramide are useful complexing agents. Esters such as amyl formate, ethyl formate, hexyl formate, propyl formate, ethyl acetate, methyl acetate, triethylene glycol diacetate and the like can be used as well. Suitable nitriles include acetonitrile, proprionitrile and the like. Suitable sulfides include dimethyl sulfide, diethyl sulfide, dibutyl sulfide, diamyl sulfide and the like.
Preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of about 75-350 and dialkyl ethers of alkylene and polyalkylene glycols. Especially preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of 125-250 and a dimethyl ether of mono-, di- or triethylene glycol. t-Butanol and glyme (1,2-dimethoxy ethane) are especially preferred.
A silane-functional complexing agent, as described in the copending application of Wehmeyer, application no. 09/574,842, entitled Method for Preparing Metal Cyanide Catalysts using Silane-functional Ligands, filed May 19, 2000, may be used instead of or in addition to the aforementioned complexing agents. As described therein, the silane-functional complexing agent may be polymerized to form a film or polymer, optionally on a support, or may function as a coupling agent to attach the catalyst complex to a support material.
In addition, the catalyst complex often contains a quantity of water that is bound into the crystalline lattice of the complex. Although the amount of bound water is difficult to determine, it is believed that this amount is typically from about 0.25 to about 3 moles of water per mole of M1 and M2 ions.
Exemplary catalysts include:
Zinc hexacyanocobaltate.zL.aH2O.nZnCl2;
Zn[Co(CN)5NO].zL.aH2O.nZnCl2;
Zns[Co(CN)6]o[Fe(CN)5NO]p.zL.aH2O.nZnCl2 (o, p=positive numbers, s=1.5o +p);
Zns[Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q.zL.aH2O.nZnCl2 (o, p, q=positive numbers, s=1.5(o+p)+q);
Zinc hexacyanocobaltate.zL.aH2O.nLaCl3;
Zn[Co(CN)5NO].zL.aH2O.nLaCl3;
Zn[Co(CN)6]o[Fe(CN)5NO]p.zL.aH2O.nLaCl3 (o, p=positive numbers, s=1.5o+p);
Zns[Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q.zL.aH2O.nLaCl3 (o, p, q=positive numbers, s=1.5(o+p)+q);
Zinc hexacyanocobaltate.zL.aH2O.nCrCl3;
Zn[Co(CN)5NO].zL.aH2O.nCrCl3;
Zns[Co(CN)6]o[Fe(CN)5NO]p.zL.aH2O.nCrCl3 (o, p=positive numbers, s=1.5o+p);
Zns[Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q.zL.aH2O.nCrCl3 (o, p, q=positive numbers, s=1.5(o+p)+q);
Magnesium hexacyanocobaltate.zL.aH2O.nZnCl2;
Mg[Co(CN)5NO].zL.aH2O.nZnCl2;
Mgs[Co(CN)6]o[Fe(CN)5NO]p.zL.aH2O.nZnCl2 (o, p=positive numbers,s=1.5o +p);
Mgs[Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q.zL.aH2O.nZnCl2 (o, p, q=positive numbers, s=1.5(o+p)+q);
Magnesium hexacyanocobaltate.zL.aH2O.nLaCl3;
Mg[Co(CN)5NO].zL.aH2O.nLaCl3;
Mgs[Co(CN)6]o[Fe(CN)5NO]p.zL.aH2O.nLaCl3 (o, p=positive numbers, s=1.5o +p);
Mgs[Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q.zL.aH2O.nLaCl3 (o, p, q=positive numbers, s=1.5(o+p)+q);
Magnesium hexacyanocobaltate.zL.aH2O.nCrCl3;
Mg[Co(CN)5NO].zL.aH2O.nCrCl3;
Mgs [Co(CN)6]o[Fe(CN)5NO]p.zL.aH2O.nCrCl3 (o, p=positive numbers, s=1.5o +p);
Mgs [Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q.zL.aH2O.nCrCl3 (o, p, q=positive numbers, s=1.5(o+p)+q);
as well as the various complexes such as are described at column 3 of U.S. Pat. No. 3,404,109, incorporated herein by reference.
The catalyst complex may be supported. One method of making a supported catalyst is by precipitating the catalyst in the presence of a polycarboxyl or polycarboxylate compound, as described in copending application of Wehmeyer, application number 09/574,848, entitled Method for Preparing Metal Cyanide Catalysts using Polycarboxylic Acids filed May 19, 2000. Supported catalysts as described in WO 99/44379 are also useful. In addition, supported catalysts can be prepared as described in the copending application of Wehmeyer, application number 09/574,842 entitled Method for Preparing Metal Cyanide Catalysts Using Silane-Functional Ligands, filed May 19, 2000.
The catalyst complex is conveniently made using standard precipitation methods as are described, for example, in U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335, 5,470,813, 5,482,908, 5,536,883, 5,589,431, 5,627,120, 5,627,122, 5,639,705, 5,714,428, 5,731,407, 5,780,584, 5,783,513, all incorporated herein by reference. In addition, the catalyst may be formed directly as a dispersion in an initiator compound, as described in copending application of Wehmeyer, application no. 09/574,847 entitled Method for Preparing Metal Cyanide Catalyst/Polyol Initiator Slurries filed May 19, 2000, or through an incipient wetness technique as described in the copending application of Molzahn et al, application no 09/574,844 entitled Incipient Wetness Method for Making Metal-Containing Cyanide Catalysts, filed May 19, 2000.
The product polyether contains one or more chains of oxyalkylene groups that are bonded to the initiator compound through a heteroatom. The heteroatom is preferably oxygen and the linkage is most preferably an ether linkage.
The product polyether is typically prepared in good yield with only small amounts of undesired by-products. In some instances, the product may contain a high molecular weight fraction that has a weight average molecular weight of 1.5X or more of that of the desired product. Typically, when this fraction is present, it constitutes about 20% or less, more typically less than about 10% of the total weight of the product.
Other than the high molecular weight fraction, the process of the invention permits the alkoxylation of a wide range of initiator compounds with the formation of few by-products. By-products other than unreacted starting materials and the high molecular weight fraction typically constitute less than about 10% by weight of the product, more typically less than about 5 weight percent and even more typically less than about 2 weight percent.
In particular, the product is characterized in that the unsaturation from the initiator compound is to a very large degree unaffected by the polymerization process. Migratable carbon-carbon unsaturation tends not to migrate under the conditions of the polymerization reaction. Hydroxyl-substituted tertiary carbon atoms adjacent to carbon-carbon unsaturation tend to be unaffected by the process, and in particular these tertiary carbons do not cleave from the adjacent unsaturated group to form by-products such as acetylene. Thus, the product of this invention typically contains no more than about 10 weight percent, preferably less than about 5 weight percent and even more preferably less than about 2 weight percent of by-products, other than unreacted starting materials and the high molecular weight fraction, based on the total weight of the product, prior to any clean-up or purification.
The product polyether is generally characterized by having a good polydispersity, typically less than about 2.0, more typically less than about 1.6 and preferably less than about 1.2, as crude products before purification to remove high molecular weight species. These polydispersities can be obtained even when the initiator contains secondary or tertiary oxyalkylatable groups.